纳米粒度和自动滴定NanoZS

1、纳米粒度及 Zeta电位分析仪光散射技术的新进展2003.101CONTENTSZetasizer range光相关光谱Photon Correlation Spectroscopy (PCS)PCS 理论概述马尔文高灵敏的粒度仪 Zetasizer (HS) 系列介绍专利的最新型检测器，激光功率多种选择Zeta 电位Zeta 电位理论概述多用途滴定器 (MPT-1)New Zeta Potential Transfer Standard (DTS0050)2THE ZETASIZER RANGE 用微量电泳法测定水和非水体系中粒子的Zeta电位Zeta 电位可权威地预测分散体系(悬浮液，乳化

2、液)的长期稳定性用光相关光谱测量分散体系中粒径分布32003年5月隆重上市世 界 顶 级 纳 米 颗 粒 和 大 分 子 特 性 分 析 仪 器纳米粒度及 Zeta电位分析仪 新一代Zetasizer Nano ZS4位于英国的马尔文公司总部5 英国马尔文仪器有限公司 _激光粒度分析仪的创始人- 世界上最大的激光粒度分析仪专业设计和生产厂家- 世界上第一台相关处理器- 世界上第一台激光衍射法粒度分析仪，- 世界上第一台激光PCS粒度分析仪- 世界上第一台超声粒度分析仪- 销售量占世界第一，仅中国大陆已有600台以上- 已获得ISO9001标准, 欧洲EMC标准认证, GMP标准认 证，唯一完全

3、符合美国FDA QSpec要求- 多方位应用支持，在中国设立正式技术服务中心.激 光 粒 度 分 析 技 术 的 先 锋6 马尔文激光粒度分析仪自80年代进入我国以来，到90年代已基本取代了传统的筛析和离心沉降方法，成为粒度分析快速、准确、高效的最佳手段。马尔文激光粒度分析仪不仅具有准确分析1m以下真实粒子的优势，而且对于透明、半透明，带色或不带色的各种乳化液和干粉的分析研究具有无可比拟的优点。7马尔文光子相关光谱仪的发展Zave = 3.6nm8世界第一台 PCS纳米粒度分析系统 (1970年) 1970年, 马尔文数字相关器，一个革命性的光子交叉相关(PCCS)数字信号处理系统，在皇家信号

4、与雷达军工实验室（Royal Signals and Radar Establishment）开发成功。世界第一台商用激光粒度分析仪及马尔文仪器公司随之诞生，并成为激光粒度分析仪技术的先锋。随后进一步开发了动态光散射的光子相关（PCS）亚微米测量技术。9Zetasizer 1000, 2000, 3000 (1997年)ZETASIZER 1000Size measurement at 90 deg. 2nm to 3 micronsZETASIZER 2000Zeta potential measurement of particles of 5nm to 30 microns size i

5、n aqueous and non aqueous systemsZETASIZER 3000Combination of 1000 and 2000 plussize measurement at 12 deg.ZETASIZER 1000 and 2000 can be upgraded to 300010ZETASIZER SeriesZETASIZER 1000 and 2000 can be upgraded to 300011Zetasizer HS系列 纳米粒度及Zeta电位分析仪和MPT-1 自动滴定系统(1999年)The MPT-1 是为Zetasizer分析仪特制的高效专

6、用自动滴定装置粒径范围：2 nm 3000 nm专利高灵敏测量系统,下限测量无须高功率激光器。2000年最新M3专利技术，具有高分辨高准确性，可分辨混合粒子1mV的Zeta电位差异。突出的高重现性，由精确的内部温控技术和在线pH测量加以保证。全自动三元滴定系统：精确控制、实时测量pH，盐浓度和电导率的连续变化。全自动结果自诊断系统：结果判断因子(RQF) 保证了每次测量质量。 内置ISO13321标准指导操作。12THE ZETASIZER RANGEINTENSITYZETASIZE 型号测量范围 PARAMETER MEASUREDYESYESYESNONOYESYESYESNONOYES

7、YES90o FIXED ALIGNMENT10001000HS S90Nano S5 to 3000nm2 to 3000nm0.6 to 6000nm2 to 3000nm13The New Zetasizer Nano seriesSizeMeasurement of colloids, emulsions and moleculesHigh sensitivity and high concentration Zeta potentialZero maintenance zeta potential measurementMolecular weightProteins and pol

8、ymers145 new instrumentsNew ZetaSize (backscatter)New Zeta & Size (backscatter)Size 90 degreesNew Zeta with 90 degree size15What Does a Conventional PCS Instrument Consist Of?PinholeDetector(Photomultiplier/AvalanchePhoto Diode)LaserSample containing particlesScattered light16WHAT DOES A PCS INSTRUM

9、ENT CONSIST OF?PinholeDetector(Photomultiplier/AvalanchePhoto Diode)LaserSample containing particlesComputercontainingcorrelator card (7132)Scattered lightZetasizer HS (High Sensitivity) instruments contain an APD detector17THE INTENSITY OF SCATTERED LIGHTThe intensity of scattered light obtained fr

10、om a dispersion of particles is dependent uponLaser wavelength Particle size 18SCATTERED LIGHT AND PARTICLE SIZEDispersion of smallparticlesLaserThe intensity of scattered light from small particlesis equal in all directions19SCATTERED LIGHT AND PARTICLE SIZEDispersion of largeparticlesThe intensity

11、 of scattered light from large particlesis not equal in all directionsLaser20BROWNIAN MOTION AND SCATTERED LIGHTBecause the scattered waves of lightare interfering with one anotherWhy does this happen?The Brownian motion of the particles causes the scattered light tofluctuate in intensity21BROWNIAN

12、MOTION AND SCATTERED LIGHTScreenTwo beams interfere andcancel each other outresulting in a decreased intensity in the scattered lightLet us consider 2 stationary particles22BROWNIAN MOTION AND SCATTERED LIGHTScreenIf the particles move,Two beams interfere andenhance each otherresulting in an increas

13、ed intensity in the scattered light23BROWNIAN MOTION AND SCATTERED LIGHTMany scattered beams interfere with one anotherresulting in a very complex intensity pattern of specklesScreenConsider many particles24Stokes-Einstein EquationD = Diffusion coefficientwhere d(H) = Hydrodynamic diameterk = Boltzm

14、anns constantT = Absolute temperatureh = Viscosityd(H) = kT3 p h D25LaserIncident BeamAxisSampleCellScreenSpecklePatternThe Speckle Pattern26Intensity FluctuationsLarge ParticlesSmall ParticlesTimeTimeIntensityIntensity27How a Correlator Works28For a system of particles undergoing Brownian motion, a

15、 speckle pattern is observed where the position of each speckle is seen to be in constant motionThe rate at which these intensity fluctuations occur will depend on the size of the particlesIntensity Fluctuations29Optical Configuration of a Backscatter DLS InstrumentAPD Detector4mW He-Ne LaserTempera

16、ture controlled cell holderAuto-attenuatorTransmission monitorMoveable measurement Position30Optical Configuration of the Zetasizer 3000APD/PM10mW He-Ne laserSize / Zetamode select90o Size cellZeta potential capillary cellCombined receiveropticsModulatorAttenuator(a) = reference beam(b) = scattering

17、 beam(b)(a)31 Zetasizer Nano series (2003年)Measurement of size, zeta potential and molecular weight of colloids and molecules 32Zetasizer Nano series Fully automated and exceptionally easy to use series of instrumentsIncorporates a combination of technologies Meets all requirements for ISO 13321, 21

18、 CFR Part 11 and has validated hardware and software33Optical Configuration of the Nano ZS34Unique Features Of NIBS Moveable measurement positionSmall particles or dilute samplesMeasure close to cell centre to maximise measurement volume and minimise flare35Concentrated samplesMeasure close to the c

19、ell wall to reduce the light path through the sample and hence minimise multiple scatteringUnique Features Of NIBS Moveable measurement position36PHOTON CORRELATION SPECTROSCOPY (PCS)光相关光谱37什么是光相关光谱( PCS)?测量纳米微粒随机运动(散射)带来的波动迁移被扫描的粒子进行着布朗运动(Brownian Motion)计算散射迁移率 测量水力直径 粒径分布应用 Stokes-Einstein方程38用PC

20、S测量小粒子散射光强度弱的原因小粒子 极稀释的样品(dilute samples)散射效果不好的粒子，(粒子的折射指数和分散相非常接近)此时用10mW 功率的He-Ne 激光就不足以PCS测量粒径。39用PCS测量小粒径时通常牺牲准确性，用增加激光能量来提高散射光强度若保持低能量激光，则因重复计算，导致结果正误差。40使用高能量激光器的缺点增加样品吸光度会导致样品发热，破坏稳定性不可预测的安全限量增加成本最好的方法是使用高灵敏监测器提高计数率41ZETASIZER HS (HIGH SENSITIVITY)马尔文推出新型光子电子计数器检测器(new generation of avalanch

21、e photodiodes (APDs)优越性：提高灵敏度可在极低浓度下测量，不需增加激光能量避免热效应，保证结果准确使用环境宽松延长仪器使用寿命，降低故障率42雪崩式光子电子计数检测器固态二极管检测器(Solid state diode detectors)当光子撞击时，产生了电子空穴对产生的高压加速了电子运动被加速的电子获的足够的能量进一步导致电离度的增加，如同雪崩一样。最初的光子能雪崩式产生大量的约106 电子这个数量级远大于普通的光电备增器( photomultiplier detector)因此有了新一代的雪崩式光子电子计数器检测器43WHATS NEW ABOUT THE APD

22、USED IN THE ZETASIZER?过去的APD价格昂贵可靠性差，尽管灵敏度高马尔文专利的新型APD，使用一种新型材料 突出的优越性：提高了可靠性，达到灵敏度与可靠性的统一减化操作缩短稳定时间(Improved settling time from power up)44应用： 小粒子和表面胶束测量胶束粒径及其分布过去这些样品要用高档4700型仪器测定20mW,488nm 氩离子激光器照射，光电倍增管检测器测定。现在仅用4 mW 就够了。45应用实例: Absorbing systemsz- 平均粒径 (nm)多分散度测定时间分计数率(KCPS)18.418.418.4345.4346

23、.0346.1180.4179.3181.2177.3177.5178.40.2460.2210.2240.1980.2120.212151515222RUN123456检测器PMPMPMAPDAPDAPD4 mW He-Ne laser 测碳黑样品计数率越高越好，结果重复性越好46应用实例: 在吸收体系中Intensity Size distribution1020% in class510501005001000Diameter (nm)4 mW He-Ne 激光 and APD 检测器测碳黑样品470.05% NONIDETz- 平均粒径 (nm)多分散度RUN123均值17.717.7

24、18.017.8 0.20.1390.1420.1380.14 0.002 测量时间 = 4 分/次Intensity Size distribution51050100Diameter (nm)1020% in class480.3% TRITON X-100Intensity Size distribution51050100Diameter (nm)1020% in class平均粒径 (nm)多分散度次数123均值8.7 0.10.0580.0650.0660.063 0.004 测量时间 = 4 分/次490.08% 吐温 20平均粒径 (nm)多分散度RUN123

25、MEAN7.7 0.20.0750.1480.0490.090 0.052 测量时间 = 4 分/次51050100粒径r (nm)1020% in classIntensity Size distribution50APPLICATIONS:Dilute systems510501005001000Diameter (nm)Intensity Size distribution1020% in classGroundwater flocculated with AlCl3 (3mg/L)z- 平均粒径 (nm)多分散度RUN123MEAN174.2174.7171.5173

26、.5 1.70.1910.1810.1860.186 0.005 测量时间 = 7 分/次51应用实例: 溶液中的蛋白质51050100500Diameter (nm)102030% in classIntensity Size distributionz- 平均粒径 (nm)多分散度RUN123MEAN10.311.411.010.9 0.50.2240.2430.2440.237 0.011 测量时间 = 15 分/次0.5% 牛血清蛋白 (BSA)52趋势分析随温度和时间的变化分析仪器内部精确控温技术，无需外部设备2 90 度范围与MPT-2联用后随pH值的变化随电导率的变化随添加剂浓度

27、的变化53Cyclosporin MicroemulsionsTime after sample preparation (hours)051520251020401008060120z-Average Diameter (nm)Formulation 1Formulation 2Formulation 3Formulation 454New MPT-2 autotitratorAutomation :pH, conductivity and additive titrationAutomation of molecular weight measurementIso-Electric Poi

28、ntApplications Sample volume less than 3ml for proteins55Zetasizer Nano S90 特点综述粒度测定范围：2nm - 3m唯一具有标准操作规程（SOP）的纳米粒度分析仪器。随时间及温度变化进行趋势分析。与自动滴定（MPT-2）相连接后，可自动测定粒度随pH、盐浓度和电导率变化的，最少仅需3ml样品。温度控制范围：2 90 C56Zetasizer Nano S90 特点综述高效率的雪崩式光电二极管(APD)检测器提供了最高的灵敏度(高于光电倍增管检测器20倍) ， 5nm以下测量无需外接高功率激光器。自动调节各种样品的最佳设置

29、在300,000:1的动态范围内自动调节激光衰减器精确的样品池温度控制2C-90C稳定的He-Ne激光器确保数据的重复性突出的高重现性，由精确的内部温控技术和在线pH测量加以保证。操作简单，无须准直、校正或保养光路密封，防止污染57Zetasizer Nano S90 特点综述- 软件：先进技术，操作简单全自动设置和测量：在仪器设置上，只需最简单的培训，包括样品池位置、衰减器设置、数据记录、分析和结果显示。测量过程中，数据的质量可通过适时的光强和数据显示评估实验结果报告。SOP: 标准的操作程序确保操作的一致性，保证重复性打印或屏幕显示报告使用简单，可进行个人化设计，只需在指定的位置选择图形和

30、输入参数，就可根据不同的需要设计不同的报告。测量数据的完全评估58Zetasizer Nano S90 特点综述- 软件：先进技术，操作简单样品数据和结果存储在测量文件中，方便进行数据的比较。数据分析数据以图形或表格的形式给出，分布算法适合各种样品包括单分散样品，宽分布样品以及多种模式样品。温度趋势分析时间趋势分析所选参数趋势分析全范围统计图59ApplicationsPaper ManufacturePharmaceutical formulationAgrochemical formulationIntravenous lipid emulsionsCeramics manufacture

31、Mineral processingDrinking Water / Waste water treatmentNon-aqueous systems60Paper manufactureThe interaction of pulp fibers, particles and other additives during the manufacturing process affects a number of important physical properties of the final product.These interactions are largely controlle

32、d by the zeta potential of the constituents.Knowledge of the zeta potential allows changes to be made to improve the quality or economy of the process .Properties affected include flocculation of the pulp, deposition on rollers and wires, filler retention and product strength.61Pharmaceutical formul

33、ationMany pharmaceutical products are formulated as emulsions and suspensions.In order to ensure efficient dosage, predictable shelf life and batch to batch consistency, particle size must be closely controlled.Zeta potential plays a large part in determining particle size. Problems such as caking,

34、creaming and changes in efficacy can be investigated by measuring the zeta potential.62Agrochemical formulation (1)A large number of agrochemicals used in spray applications are formulated as granules. These have to form stable dispersions for hours when added to the water available locally to the f

35、armer. Formulations will be different in, say, England and Egypt as the water available contains different ions in different concentrationsThe formulation has to include surfactants to aid dispersion when the granules are dispersed in water63Agrochemical formulation (2)The type and concentration of

36、surfactant are critical. Without some fundamental measurement the choice is a matter of experience and trial and error.Formulation becomes more complicated as an optimum formulation will often require two surfactants.Measurement of zeta potential provides a parameter measured in seconds which indica

37、tes the stability of the dispersion when prepared for use.64Intravenous lipid emulsionsThese are usually known under the trade name of 慖ntralipid?emulsions, they are used to feed patients through an intravenous drip when food cannot be taken by mouth.For adequate nutrition the body requires fats, su

38、gars, amino acids and minerals. Rather than introduce each of these into the body separately, it is obviously more convenient to mix everything into one bag to use in a single drip.This causes difficulties as a mixture of these components will almost certainly cause flocculation of the fat emulsion.

39、 Measurement of the zeta potential of the fat emulsion with addition of each of the additives has been found to be the best way of formulating these systems.65Ceramics manufacture (1)Ceramics fall into two general categories, technical or engineering ceramics and 憌hitewareIn both cases, the particle

40、 size distribution and the stability of the dispersion as the 憇lip? determines properties of the final product.The thickness and density of the product and the size of voids will all be affected.66Ceramics manufacture (2)The usual method of formulation involves adding polymer as a dispersing agentTh

41、is is a simple solution to the dispersion problem but has several disadvantages; burning the polymer out during firing causes shrinkage and voids and in addition is costly.Improving the dispersion using electrostatic forces may involve merely changing the concentration of a few ions in the system.Th

42、is will potentially lead to denser and hence stronger and more consistent product 67Mineral processing (1)A large proportion of the separation of useful minerals from the useless 慻angue?is done using a technique called 慒roth flotationThe mineral is finely ground, added to water and the environment m

43、odified such that the target mineral will adhere to collector oils bubbled through the dispersion. The oil and mineral float to the surface to be skimmed off.The conditions can now be modified to float a different mineral68Mineral processing (2)The controlling parameter that determines the efficiency of this process is the zeta potential.By measuring the zeta potential the optimum conditions and concentration of additives can be determined to maximise recovery efficien